224 research outputs found
Percolation of Immobile Domains in Supercooled Thin Polymeric Films
We present an analysis of heterogeneous dynamics in molecular dynamics
simulations of a thin polymeric film, supported by an absorbing structured
surface. Near the glass transition "immobile" domains occur throughout the
film, yet the probability of their occurrence decreasing with larger distance
from the surface. Still, enough immobile domains are located near the free
surface to cause them to percolate in the direction perpendicular to surface,
at a temperature near the glass transition temperature. This result is in
agreement with a recent theoretical model of glass transition
The Aggregation Kinetics of a Simulated Telechelic Polymer
We investigate the aggregation kinetics of a simulated telechelic polymer
gel. In the hybrid Molecular Dynamics (MD) / Monte Carlo (MC) algorithm,
aggregates of associating end groups form and break according to MC rules,
while the position of the polymers in space is dictated by MD. As a result, the
aggregate sizes change every time step. In order to describe this aggregation
process, we employ master equations. They define changes in the number of
aggregates of a certain size in terms of reaction rates. These reaction rates
indicate the likelihood that two aggregates combine to form a large one, or
that a large aggregate splits into two smaller parts. The reaction rates are
obtained from the simulations for a range of temperatures.
Our results indicate that the rates are not only temperature dependent, but
also a function of the sizes of the aggregates involved in the reaction. Using
the measured rates, solutions to the master equations are shown to be stable
and in agreement with the aggregate size distribution, as obtained directly
from simulation data. Furthermore, we show how temperature induced variations
in these rates give rise to the observed changes in the aggregate distribution
that characterizes the sol-gel transition.Comment: 9 pages, 10 figure
Individual Entanglements in a Simulated Polymer Melt
We examine entanglements using monomer contacts between pairs of chains in a
Brownian-dynamics simulation of a polymer melt. A map of contact positions with
respect to the contacting monomer numbers (i,j) shows clustering in small
regions of (i,j) which persists in time, as expected for entanglements. Using
the ``space''-time correlation function of the aforementioned contacts, we show
that a pair of entangled chains exhibits a qualitatively different behavior
than a pair of distant chains when brought together. Quantitatively, about 50%
of the contacts between entangled chains are persistent contacts not present in
independently moving chains. In addition, we account for several observed
scaling properties of the contact correlation function.Comment: latex, 12 pages, 7 figures, postscript file available at
http://arnold.uchicago.edu/~ebn
Growth, microstructure, and failure of crazes in glassy polymers
We report on an extensive study of craze formation in glassy polymers.
Molecular dynamics simulations of a coarse-grained bead-spring model were
employed to investigate the molecular level processes during craze nucleation,
widening, and breakdown for a wide range of temperature, polymer chain length
, entanglement length and strength of adhesive interactions between
polymer chains. Craze widening proceeds via a fibril-drawing process at
constant drawing stress. The extension ratio is determined by the entanglement
length, and the characteristic length of stretched chain segments in the
polymer craze is . In the craze, tension is mostly carried by the
covalent backbone bonds, and the force distribution develops an exponential
tail at large tensile forces. The failure mode of crazes changes from
disentanglement to scission for , and breakdown through scission
is governed by large stress fluctuations. The simulations also reveal
inconsistencies with previous theoretical models of craze widening that were
based on continuum level hydrodynamics
Why is Understanding Glassy Polymer Mechanics So Difficult?
In this Perspective, I describe recent work on systems in which the
traditional distinctions between (i) unentangled vs. well-entangled systems and
(ii) melts vs. glasses seem least useful, and argue for the broader use in
glassy polymer mechanics of two more dichotomies: systems which possess (iii)
unary vs. binary and (iv) cooperative vs. nonccoperative relaxation dynamics. I
discuss the applicability of (iii-iv) to understanding the functional form of
glassy strain hardening. Results from molecular dynamics simulations show that
the "dramatic" strain hardening observed in densely entangled systems is
associated with a crossover from unary, noncooperative to binary, cooperative
relaxation as strain increases; chains stretch between entanglement points,
altering the character of local plasticity. Promising approaches for future
research along these lines are discussed.Comment: Results and conclusions same but manuscript extensively edited for
clarity. Accepted for publication in J. Polym. Sci. - Polym. Phy
Shear yielding of amorphous glassy solids: Effect of temperature and strain rate
We study shear yielding and steady state flow of glassy materials with
molecular dynamics simulations of two standard models: amorphous polymers and
bidisperse Lennard-Jones glasses. For a fixed strain rate, the maximum shear
yield stress and the steady state flow stress in simple shear both drop
linearly with increasing temperature. The dependence on strain rate can be
described by a either a logarithm or a power-law added to a constant. In marked
contrast to predictions of traditional thermal activation models, the rate
dependence is nearly independent of temperature. The relation to more recent
models of plastic deformation and glassy rheology is discussed, and the
dynamics of particles and stress in small regions is examined in light of these
findings
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